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United States Patent |
5,183,869
|
Kramer
,   et al.
|
February 2, 1993
|
Hardenable compositions
Abstract
Compositions comprising
A) compounds of formula I
##STR1##
wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are identical or different
and each is hydrogen or methyl, and X is a divalent organic radical
comprising from 2 to 60 carbon atoms, and
B) compounds of formula II
##STR2##
wherein R.sub.5 and R.sub.6 are identical or different and each,
independently of the other, is C.sub.1 -C.sub.8 alkyl, and Y is hydrogen
or an allyl radical, are distinguished by a favorable processing behaviour
and high glass transition temperatures.
Inventors:
|
Kramer; Andreas (Dudingen, CH);
Brunner; Rudolf (Belfaux, CH);
Zahir; Abdul-Cader (Oberwil, CH)
|
Assignee:
|
Ciba-Geigy Corporation (Ardsley, NY)
|
Appl. No.:
|
699541 |
Filed:
|
May 14, 1991 |
Foreign Application Priority Data
Current U.S. Class: |
526/262 |
Intern'l Class: |
C08F 026/06 |
Field of Search: |
526/262
|
References Cited
U.S. Patent Documents
4100140 | Jul., 1978 | Zahir et al. | 526/90.
|
4288583 | Sep., 1981 | Zahir et al. | 526/262.
|
4371719 | Feb., 1983 | Zahir et al. | 568/723.
|
4812511 | Mar., 1989 | Domeier | 524/850.
|
4853449 | Aug., 1989 | Domeier | 526/259.
|
Foreign Patent Documents |
1139592 | Dec., 1968 | GB.
| |
348345 | Jun., 1988 | GB | 526/262.
|
Primary Examiner: Schofer; Joseph L.
Assistant Examiner: Walker; Alex H.
Attorney, Agent or Firm: Villamizar; JoAnn
Claims
What is claimed is:
1. A composition comprising:
(A) a compound of formula I
##STR9##
wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are identical or different
and each is hydrogen or methyl, and X is a divalent organic radical
comprising 2 to 60 carbon atoms,
(B) a compound of formula II
##STR10##
wherein R.sub.5 and R.sub.6 are identical or different and each,
independently of the other, is C.sub.1 -C.sub.8 alkyl, and Y is hydrogen
or an allyl radical, and
(C) an alkenylphenol of formula IV, V or VI
##STR11##
wherein each of R.sub.11, R.sub.12 and R.sub.13, independently of the
others, is a hydrogen atom or a C.sub.3 -C.sub.10 alkenyl group, at least
one of the radicals R.sub.11 to R.sub.13 being an alkenyl group, and Z is
hydrogen, C.sub.1 -C.sub.10 alkyl, C.sub.6 -C.sub.10 aryl or C.sub.3
-C.sub.10 alkenyl,
##STR12##
wherein Q is a direct bond, methylene, 2,2-propylidene, --CO--, --O--,
--S--, --SO-- or --SO.sub.2 --, and each of R.sub.14, R.sub.15, R.sub.16
and R.sub.17, independently of the others, is a hydrogen atom or a C.sub.3
-C.sub.10 alkenyl group, at least one of the radicals R.sub.14 to R.sub.17
being an alkenyl group, and Z is hydrogen, C.sub.1 -C.sub.10 alkyl,
C.sub.6 -C.sub.10 aryl or C.sub.3 -C.sub.10 alkenyl,
##STR13##
wherein each of R.sub.18, R.sub.19, R.sub.20, R.sub.21, R.sub.22 and
R.sub.23, independently of the others, is a hydrogen atom, C.sub.1
-C.sub.4 alkyl or C.sub.3 -C.sub.10 alkenyl, at least one of the radicals
R.sub.18 to R.sub.23 being an alkenyl group, and a is a number from 0 to
10, and Z is hydrogen, C.sub.1 -C.sub.10 alkyl, C.sub.6 -C.sub.10 aryl or
C.sub.3 -C.sub.10 alkenyl.
2. A composition according to claim 1 comprising a compound of formula I
wherein X is --(CH.sub.2).sub.p --, with p=from 2 to 20, phenylene,
xylylene, naphthylene, cyclopentylene, 1,5,5-trimethylcyclohexylene-1,3;
cyclohexylene-1,4; 1,4-bis(methylene)cyclohexylene, the radical of
4,4'-bicyclohexylmethane or a group of formula III
##STR14##
wherein R.sub.7 and R.sub.8 are identical or different and each is
hydrogen or C.sub.1 -C.sub.4 alkyl, each of R.sub.9 and R.sub.10,
independently of the other, is a hydrogen or halogen atom, and T is
methylene, 2,2-propylidene, --CO--, --O--, --S-- or --SO.sub.2 --.
3. A composition according to claim 1 comprising a compound of formula I
wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are hydrogen.
4. A composition according to claim 1 comprising a compound of formula I
wherein X is hexamethylene, trimethylhexamethylene,
1,5,5-trimethylcyclohexylene-1,3; the radical of 4,4'-bicyclohexylmethane
or a group of formula III where T is methylene, 2,2-propylidene, --O-- or
--S--.
5. A composition according to claim 1 comprising a compound of formula I
wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are hydrogen and X is a
group of formula III wherein R.sub.7 and R.sub.8 are identical or
different and each is hydrogen, methyl or ethyl, R.sub.9 and R.sub.10 are
hydrogen and T is methylene.
6. A composition according to claim 1 comprising a compound of formula II
wherein R.sub.5 and R.sub.6 are methyl and Y is hydrogen or an allyl
radical.
7. A composition according to claim 1 comprising, per mole of component A,
from 0.027 to 1.15 mol, preferably from 0.045 to 0.9 mol, of component B.
8. A composition according to claim 1 wherein, in the formulae IV to VI,
the alkenyl group is an allyl, methallyl or 1-propenyl group.
9. A composition according to claim 1 comprising an alkenylphenol of
formula V wherein Q is methylene, 2,2-propylidene, --O--, --S--, --CO-- or
--SO.sub.2 --, each of R.sub.14 and R.sub.16 is an allyl radical and each
of R.sub.15 and R.sub.17 is a hydrogen atom, and Z is hydrogen.
10. A composition according to claim 1 comprising an alkenylphenol of
formula V wherein Q is 2,2-propylidene, each of R.sub.14 and R.sub.16 is
an allyl radical and each of R.sub.15 and R.sub.17 is a hydrogen atom, and
Z is hydrogen.
11. A composition according to claim 1 comprising, per mole of
alkenylphenol, from 0.1 to 2 mol, preferably from 0.2 to 0.5 mol, of
component B.
12. A process for the preparation of hardened products using a composition
according to claim 1.
Description
The present invention relates to compositions comprising bismaleimides and
2,6-dialkyl-4-allylphenols or 2,6-dialkyl-4-allylphenol allyl ethers and
to a process for the preparation of hardened products using the
compositions according to the invention.
Compositions based on bismaleimides and alkenylphenols are generally known
to the person skilled in the art. U.S. Pat. No. 4,100,140 and U.S. Pat.
No. 4,288,583 may be cited as examples of such bismaleimide systems. The
known hardenable mixtures, however, do not satisfy the stringent
requirements, for example regarding processing behaviour, in every respect
since they are generally highly viscous mixtures even at the processing
temperature. In addition, bismaleimides tend to crystallise out in such
systems.
It has now been found that bismaleimide systems modified with
2,6-dialkyl-4-allylphenol or 2,6-dialkyl-4-allylphenol allyl ether have a
significantly lower system viscosity, which is advantageous for
processing. At elevated temperature, such compositions have a longer, and
accordingly more favourable, pot life. It has also been found that the
compositions are stable at the processing temperature (from 80.degree. to
130.degree. C.) and also at room temperature, that is to say, the
bismaleimide does not crystallise out. Surprisingly, however, it has now
also been observed that the hardened products based on the compositions
according to the invention have a significantly higher glass transition
temperature.
The present invention accordingly relates to compositions comprising
A) compounds of formula I
##STR3##
wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are identical or different
and each is hydrogen or methyl, and X is a divalent organic radical
comprising from 2 to 60 carbon atoms, and
B) compounds of formula II
##STR4##
wherein R.sub.5 and R.sub.6 are identical or different and each,
independently of the other, is C.sub.1 -C.sub.8 alkyl, and Y is hydrogen
or an allyl radical.
The bismaleimides of formula I are known compounds and are described, for
example, in U.S. Pat. No. 4,100,140. They are preferably compounds of
formula I wherein X is --(CH.sub.2).sub.p --, with p=from 2 to 20,
phenylene, xylylene, naphthylene, cyclopentylene,
1,5,5-trimethylcyclohexylene-1,3; cyclohexylene-1,4;
1,4-bis(methylene)cyclohexylene, the radical of 4,4'-bicyclohexylmethane
or a group of formula III
##STR5##
wherein R.sub.7 and R.sub.8 are identical or different and each is
hydrogen or C.sub.1 -C.sub.4 alkyl, each of R.sub.9 and R.sub.10,
independently of the other, is a hydrogen or halogen atom, and T is
methylene, 2,2-propylidene, --CO--, --O--, --S-- or --SO.sub.2 --. Also
preferred are compounds of formula I wherein R.sub.1, R.sub.2, R.sub.3 and
R.sub.4 are hydrogen.
Especially preferred are compounds of formula I wherein X is hexamethylene,
trimethylhexamethylene, 1,5,5-trimethylcyclohexylene-1,3; the radical of
4,4'-bicyclohexylmethane or a group of formula III wherein T is methylene,
2,2-propylidene, --O-- or --S--.
There are especially used compounds of formula I wherein R.sub.1, R.sub.2,
R.sub.3 and R.sub.4 are hydrogen and X is a group of formula III wherein
R.sub.7 and R.sub.8 are identical or different and each is hydrogen,
methyl or ethyl, R.sub.9 and R.sub.10 are hydrogen and T is methylene.
It is, of course, also possible to use mixtures of two or more different
bismaleimides. Preference is given to mixtures of
N,N'-4,4'-diphenylmethane bismaleimide and compounds of formula I wherein
R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are hydrogen and X is a group of
formula III wherein R.sub.7 and R.sub.8 are identical or different and
each is methyl or ethyl, R.sub.9 and R.sub.10 are hydrogen and T is
methylene. The molar ratio of the unsubstituted to the substituted
bismaleimides is in this case preferably from 1:0.8 to 1.2.
Examples of bismaleimides of formula I are: N,N'-ethylene bismaleimide,
N,N'-hexamethylene bismaleimide, N,N'-trimethylhexylene bismaleimide,
N,N'-m-phenylene bismaleimide, N,N'-4,4'-diphenylmethane bismaleimide,
N,N'-4,4'-diphenyl ether bismaleimide,
N,N'-(1,5,5-trimethylcyclohexylene-1,3) bismaleimide,
N,N'-4,4'-dicyclohexylmethane bismaleimide, N,N'-p-xylylene bismaleimide,
N,N'-4,4'-di-(2-ethyl-6-methylphenyl)methane bismaleimide,
N,N'-4,4'-di-(2,6-dimethylphenyl)methane bismaleimide,
N,N'-4,4'-di-(2,6-diethylphenyl)methane bismaleimide,
N,N'-4,4'-di-(2,6-diisopropylphenyl)methane bismaleimide,
N,N'-4,4'-di-(2-ethyl-6-isopropylphenyl)methane bismaleimide and
N,N'-4,4'-di-(3-chloro-2,6-diethylphenyl)methane bismaleimide.
The preparation of the compounds according to formula I is known and is
carried out, for example, by reacting the unsubstituted or substituted
maleic acid anhydride with the corresponding diamines. Customary methods
are described in U.S. Pat. No. 3,010,290 or GB-PS 1 137 592.
The compounds of formula II are also known compounds. Their preparation is
generally known to the person skilled in the art. The
2,6-dialkyl-4-allylphenol allyl ethers are described, for example, in
Helv. Chem. Acta 56, 14 (1973).
Compounds of formula II wherein R.sub.5 and R.sub.6 are methyl and Y is
hydrogen or an allyl radical are preferred.
Examples of suitable phenols are 2,6-dimethyl-4-allylphenol,
2,6-diethyl-4-allylphenol, 2,6-dipropyl-4-allylphenol,
2,6-diisopropyl-4-allylphenol, 2,6-di-(1-methylpropyl)-4-allylphenol,
2,6-diisobutyl-4-allylphenol and 2,6-dihexyl-4-allylphenol as well as the
allyl ethers of those compounds.
In general, the compositions according to the invention comprise, per mole
of component A, from 0.027 to 1.15 mol, preferably from 0.045 to 0.9 mol,
of component B.
The mixtures according to the invention may also comprise alkenylphenols of
formula IV, V or VI:
##STR6##
wherein each of R.sub.11, R.sub.12 and R.sub.13, independently of the
others, is a hydrogen atom or a C.sub.3 -C.sub.10 alkenyl group, at least
one of the radicals R.sub.11 to R.sub.13 being an alkenyl group, and Z is
hydrogen, C.sub.1 -C.sub.10 alkyl, C.sub.6 -C.sub.10 aryl or C.sub.3
-C.sub.10 alkenyl,
##STR7##
wherein Q is a direct bond, methylene, 2,2-propylidene, --CO--, --O--,
--S--, --SO-- or --SO.sub.2 -- and each of R.sub.14, R.sub.15, R.sub.16
and R.sub.17, independently of the others, is a hydrogen atom or a C.sub.3
-C.sub.10 alkenyl group, at least one of the radicals R.sub.14 to R.sub.17
being an alkenyl group, and Z is hydrogen, C.sub.1 -C.sub.10 alkyl,
C.sub.6 -C.sub.10 aryl or C.sub.3 -C.sub.10 alkenyl, or
##STR8##
wherein each of R.sub.18, R.sub.19, R.sub.20, R.sub.21, R.sub.22 and
R.sub.23, independently of the others, is a hydrogen atom, C.sub.1
-C.sub.4 alkyl or C.sub.3 -C.sub.10 alkenyl, at least one of the radicals
R.sub.18 to R.sub.23 being an alkenyl group, and a is a number from 0 to
10, and Z is hydrogen, C.sub.1 -C.sub.10 alkyl, C.sub.6 -C.sub.10 aryl or
C.sub.3 -C.sub.10 alkenyl.
The compounds of formulae IV to VI preferably comprise an allyl, methallyl
or 1-propenyl radical as alkenyl group.
Of the compounds of formulae IV to VI, there are preferably used in the
compositions according to the invention compounds of formula V wherein Q
is methylene, 2,2-propylidene, --O--, --S--, --CO-- or --SO.sub.2 --, each
of R.sub.14 and R.sub.16 is an allyl radical and each of R.sub.15 and
R.sub.17 is a hydrogen atom, and Z is hydrogen.
Alkenylphenols of formula V wherein Q is 2,2-propylidene, each of R.sub.14
and R.sub.16 is an allyl radical and each of R.sub.15 and R.sub.17 is a
hydrogen atom, and Z is hydrogen are especially preferred.
The compositions according to the invention generally comprise, per mole of
alkenylphenyl, from 0.1 to 2 mol, preferably from 0.2 to 0.5 mol, of
component B.
Examples of alkenyl-substituted phenols and polyols are, for example,
o,o'-diallyl bisphenol A, 4,4'-dihydroxy-3,3'-diallylbiphenyl,
bis(4-hydroxy-3-allylphenyl)methane,
2,2-bis(4-hydroxy-3,5-diallylphenyl)propane, eugenol
(4-allyl-2-methoxyphenol), o,o'-dimethyllyl bisphenol A,
4,4'-dihydroxy-3,3'-dimethallylbiphenyl,
bis(4-hydroxy-3-methallylphenyl)methane,
2,2-bis(4-hydroxy-3,5-dimethallylphenyl)propane,
4-methallyl-2-methoxyphenol, 2,2-bis(4-methoxy-3-allylphenyl)propane,
2,2-bis(4-methoxy-3-methallylphenyl)propane,
4,4'-dimethoxy-3,3'-diallylbiphenyl,
4,4'-dimethoxy-3,3'-dimethallylbiphenyl,
bis(4-methoxy-3-allylphenyl)methane,
bis(4-methoxy-3-methallylphenyl)methane,
2,2-bis(4-methoxy-3,5-diallylphenyl)propane,
2,2-bis(4-methoxy-3,5-dimethallylphenyl)propane, 4-allylveratrole
(4-allyl-1,2-dimethoxybenzene) and 4-methallylveratrole
(4-methallyl-1,2-dimethoxybenzene).
The preparation of the alkenylphenols is known and is effected, for
example, by reacting the corresponding phenols and, for example, allyl
chloride in the presence of an alkali metal hydroxide in a suitable
solvent, the products obtained then being subjected to a Claisen
rearrangement. Methods of that type are described, for example, in U.S.
Pat. Nos. 4,100,140 and 4,288,583.
The compositions according to the invention can be prepared simply by
mixing the components together, or by heating the composition at from
75.degree. to 140.degree. C. for approximately from 15 to 60 minutes. In
order to facilitate the reaction, it is also possible optionally to use
solvents, especially volatile solvents, such as chlorinated hydrocarbons,
esters, ether alcohols or tetrahydrofuran. The solvent is removed after
the reaction.
The hardening of the compositions according to the invention generally
takes place at temperatures of from 100.degree. to 300.degree. C. for a
period sufficient to achieve hardening.
During hardening, a network is formed with a high cross-linking density.
The term "hardening" used here accordingly denotes the conversion of the
low-viscosity resin mixtures into insoluble and non-metable cross-linked
products. High-performance materials can thus be produced, such as, for
example, fibre-reinforced composites, structural adhesives, laminating
resins or electroresins, which can be exposed to high temperatures.
In any processing phase before hardening, the compositions according to the
invention can be mixed with customary modifiers, such as, for example,
extenders, fillers and reinforcing agents, pigments, dyestuffs, organic
solvents, plasticisers, agents for improving the dry-tackiness,
(tackifiers), gums or accelerators. Suitable extenders, reinforcing
agents, fillers and pigments are, for example: coal-tar, bitumen, glass
fibres, boron fibres, carbon fibres, cellulose, polyethylene powder,
polypropylene powder, mica, asbestos, quartz powder, gypsum, antimony
trioxide, bentonites, silicon dioxide aerogel ("Aerosil"), lithopone,
barite, titanium dioxide, carbon black, graphite, iron oxide or metal
powders, such as, for example, aluminium or iron powder. Other customary
additives, such as, for example, flame retardants, thixotropic agents,
flow control agents, such as silicones, cellulose acetate butyrate,
polyvinyl butyrate, waxes, stearates and the like (which can in some cases
also be used as mould release agents) may also be added to the hardenable
mixtures.
The hardenable compositions can be prepared in customary manner using known
mixing units, such as stirrers, kneaders, roller bodies and the like.
The compositions according to the invention are distinguished by a very
good processing behavior, good solubility in customary organic solvents,
good stability in the melt or in solution and by good thermal and
mechanical properties of the hardened products. The products obtained also
have good electrical properties, have high glass transition temperatures
and are not brittle. The compositions according to the invention can also
be used without difficulty as melts, for example for impregnation.
The present invention accordingly relates also to a process for the
preparation of hardened products using the compositions according to the
invention.
The described compositions according to the invention can be used in
various fields, such as, for example, in prepregs, laminates, composites,
printed circuit boards, castings, moulded articles, adhesives and
coatings. Their use in the manufacture of fibre-reinforced composites,
which are very important in the aeronautical industry, is of particular
interest. For example, the modified resins can be used to preimpregnate
various fibrous materials that are used as honeycomb skins or as
structural parts. Processes for the manufacture of prepregs are known to
the person skilled in the art. There may be used as fibrous materials, for
example, graphite, glass and Kevlar. Processes for the manufacture of
laminates are also known. Laminates of various thicknesses can be
manufactured, for example, by compression moulding or autoclave moulding.
The mixtures according to the invention can also be used successfully as
adhesion-promoters.
Some preferred embodiments of the present invention are described in the
following Examples.
EXAMPLE 1
A mixture of 100 g of N,N'-4,4'-diphenylmethane bismaleimide, 65.4 g of
o,o'-diallyl bisphenol A and 10 g of 2,6-dimethyl-4-allylphenol is melted
at from 120.degree. to 130.degree. C. A homogeneous mixture which is
highly viscous at room temperature and having .eta..sub.100 =190 mPa.s and
a gelling time of 28 minutes at 160.degree. C. is obtained.
The resin composition, which exhibits low viscosity at 120.degree. C., is
poured into a metal mould 4 mm thick and hardened for 1 hour at
180.degree. C., for 2 hours at 200.degree. C. and for 6 hours at
250.degree. C. After cooling, the transparent polymer plate is cut into
test rods using which the following properties are measured:
______________________________________
T.sub.g onset : 315.degree. C.
flexural strength: 187 MPa
(in accordance with ISO 178)
edge fibre elongation: 7.2%
(in accordance with ISO 178)
______________________________________
[T.sub.g onset is the point of intersection of the extended base line with
the tangent at the measuring curve in the area of the steepest rise
(measured using TMA, Mettler TA 3000)]
EXAMPLE 2
A mixture of 100 g of N,N'-4,4'-diphenylmethane bismaleimide, 56.0 g of
o,o'-diallyl bisphenol A and 12.4 g of 2,6-dimethyl-4-allylphenol allyl
ether is melted at from 120.degree. C. to 130.degree. C. A homogeneous
mixture which is highly viscous at room temperature and having
.eta..sub.100 =140 mPa.s and a gelling time of 31 minutes at 160.degree.
C. is obtained.
The resin composition, which exhibits low viscosity at 120.degree. C., is
poured into a metal mould 4 mm thick and hardened for 1 hour at
180.degree. C., for 2 hours at 200.degree. C. and for 6 hours at
250.degree. C. After cooling, the transparent polymer plate is cut into
test rods using which the following properties are measured:
______________________________________
T.sub.g onset : 317.degree. C.
flexural strength: 166 MPa
(in accordance with ISO 178)
edge fibre elongation: 5.2%
(in accordance with ISO 178)
______________________________________
EXAMPLE 3
A mixture of 100 g of N,N'-4,4'-diphenylmethane bismaleimide, 62.8 g of
o,o'-diallyl bisphenol A and 16.4 g of 2,6-dimethyl-4-allylphenol allyl
ether is melted at from 120.degree. to 130.degree. C. A homogeneous
mixture which is highly viscous at room temperature and having
.eta..sub.100 =90 mPa.s and a gelling time of 31 minutes at 160.degree. C.
is obtained.
The resin composition, which exhibits low viscosity at 120.degree. C., is
poured into a metal mould 4 mm thick and hardened for 1 hour at
180.degree. C., for 2 hours at 200.degree. C. and for 6 hours at
250.degree. C. After cooling, the transparent polymer plate is cut into
test rods using which the following properties are measured:
______________________________________
T.sub.g onset : 326.degree. C.
flexural strength: 153 MPa
(in accordance with ISO 178)
edge fibre elongation: 5.2%
(in accordance with ISO 178)
______________________________________
EXAMPLE 4
A mixture of 50 g of N,N'-4,4'-diphenylmethane bismaleimide, 50 g of
N,N'-4,4'-di-(2-ethyl-6-methylphenyl)methane bismaleimide, 58 g of
o,o'-diallyl bisphenol A and 10 g of 2,6-dimethyl-4-allylphenol allyl
ether is melted at from 120.degree. to 130.degree. C. A homogeneous
mixture which is highly viscous at room temperature and having
.eta..sub.100 =200 mPa.s and a gelling time of 31 minutes at 160.degree.
C. is obtained.
The resin composition, which exhibits low viscosity at 120.degree. C., is
poured into a metal mould 4 mm thick and hardened for 1 hour at
180.degree. C., for 2 hours at 200.degree. C. and for 6 hours at
250.degree. C. After cooling, the transparent polymer plate is cut into
test rods using which the following properties are measured:
______________________________________
T.sub.g onset : 294.degree. C.
flexural strength: 144 MPa
(in accordance with ISO 178)
edge fibre elongation: 4.8%
(in accordance with ISO 178)
______________________________________
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